CN102432989A - Flame-resistant polycarbonate resin composition - Google Patents

Flame-resistant polycarbonate resin composition Download PDF

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CN102432989A
CN102432989A CN201110364807XA CN201110364807A CN102432989A CN 102432989 A CN102432989 A CN 102432989A CN 201110364807X A CN201110364807X A CN 201110364807XA CN 201110364807 A CN201110364807 A CN 201110364807A CN 102432989 A CN102432989 A CN 102432989A
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composition
phenyl
acid
polycarbonate resin
butyl
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大平洋二
友田琢也
品川佳久
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Teijin Ltd
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Teijin Chemicals Ltd
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Abstract

To provide a flame-resistant polycarbonate resin composition having prescribed-range transparency and having excellent flame resistance. This flame-resistant polycarbonate resin composition contains 0.1-0.2 pt.wt. of polytetrafluoroethylene (B component) having fibril-forming capability and 0.001-20 pts.wt. of a flame retardant (C component) based on 100 pts.wt. of an aromatic polycarbonate-based resin (A component).

Description

Flame-retardant polycarbonate resin composition
The application be that May 26, application number in 2008 are 200810098983.1 the applying date, denomination of invention divides an application for the application of " flame-retardant polycarbonate resin composition ".
Technical field
The present invention relates to a kind of flame-retardant polycarbonate resin composition.More particularly, the flame-retardant polycarbonate resin composition that relates to a kind of transparency and excellent in flame retardance.
Background technology
Because aromatic polycarbonate resin not only has the transparency or excellent thermotolerance and intensity, but also has certain flame retardant resistance, thereby it is widely used in every field.But, the raising of the flame retardant resistance grade that causes with respect to the thin-walled property of raising that requires because of the flame retardant resistance of electronic apparatus machine part, OA associated components etc. in recent years or goods, the flame retardant resistance of talkative aromatic polycarbonate resin is very inabundant.And, require to have the high flame retardant that meets V-0 among UL specification (American insurance dealer's proof test institute (the Underwriters Laboratories Inc))-94 recently under many circumstances, thereby the PC material of having given high fire resistance seems extremely important.
In order to obtain high flame retardant, for example, drippage (drip) phenomenon of the resin when suppressing combustion test is important.As the method that suppresses drip phenomenon; Known have as matrix resin use method, use the method for the polycarbonate resin of copoly type, add as Antidrip agent and have (with reference to the patent documentations 1～3) such as methods that fibril forms the tetrafluoroethylene (below, abbreviate fibrillation PTFE sometimes as) of ability as matrix resin with the unitary aromatic polycarbonate resin of side chain.
Wherein, Use has the method for the unitary aromatic polycarbonate resin of side chain as matrix resin; Though can expect to keep the transparency and have certain anti-drippage effect,, the mobile shortcoming that reduces is arranged; If in the time of will suppressing the reduction (minimizing) of flowability, exist the problem that loses anti-drippage effect again with respect to the unitary amount of the side chain of resin total amount.Use the method for the polycarbonate resin of copoly type as matrix resin, because its method of manufacture is special, it is poor to make efficient, thereby, not only aspect practicality or the economy problem is being arranged, but also existing the problem that can not obtain anti-fully drippage effect.And the method for adding fibrillation PTFE owing to obtain anti-drippage effect easily, and is added fibrillation PTFE and the reduction of the flowability that causes is also few, thereby it is applicable in the material (material with UL specification V-0, V-1) that requires high flame retardant more.But, the problem that it has the transparency to reduce.
In addition, the reduction of the transparency, the problem that not only has light transmission to reduce also is attended by the defective that the design space of the painted grade of the so-called part that comprises sensation diminishes.See conversely, then we can say the material that keeps the transparency, that is, the material that the total light transmittance in the moulding article is high, its design space of part that comprises sensation is big.Particularly; For the high material of total light transmittance; Can use dyestuff is that tinting material is given transparent color (being commonly referred to as bone look (skeleton color)); Further, can be coloured material combination or to use pigment separately be coloured material and give translucent color or opaque color also with pigment.And, can make light diffusing obtain to express through adding light diffusing agent, can give the light diffusing of targeted degree through the control addition.Therefore, the reduction of the transparency also is the reduction of transmittance, the painted difficulty that becomes that can make transparent color, thus make the part that comprises sensation and diminish the design space that further comprises the painted integral body of giving light diffusing.
Patent documentation 1:JP spy opens the 2007-31538 communique
Patent documentation 2:JP spy opens flat 07-258532 communique
Patent documentation 3:JP spy opens flat 11-323118 communique
Summary of the invention
The object of the present invention is to provide a kind of flame-retardant polycarbonate resin composition that can satisfy the transparency (total light transmittance) of excellent flame and certain limit simultaneously.
In order to solve the problems referred to above in the method for adding fibrillation PTFE; The inventor etc. have carried out concentrated research, and its result finds, is limited to the specified range of a small amount of scope through the addition with fibrillation PTFE; Can satisfy anti-fully drippage effect simultaneously; Also promptly can satisfy sufficient flame retardant resistance and certain total light transmittance, can keep the painted design space that comprises the sensation part simultaneously and the appearance design that obtains uniqueness, thereby accomplish the present invention.Promptly; Through adding the transmittance that a spot of fibrillation PTFE expresses (when the time for the thick profiled sheeting of 2mm with limited range; Total light transmittance is 74～87%) the aromatic polycarbonate resin material, the little by little atomizing that causes because of its a spot of fibrillation PTFE can bring unique " sending out the transparency of mist " high aesthetic appearance.And, find when this material of use, can keep and comprise painted design space sensation, functional part fully.
According to the present invention, a kind of flame retardant resin composition is provided, this resin combination comprises: aromatic polycarbonate resins (A composition) 100 weight parts; Have fibril form ability tetrafluoroethylene, be preferably the tetrafluoroethylene (B composition) that fibril forms ability that has of mixed style, it is 0.1～0.2 weight part with respect to aromatic polycarbonate resins (A composition) 100 weight parts; And fire retardant (C composition), it is 0.001～20 weight part with respect to aromatic polycarbonate resins (A composition) 100 weight parts.
Flame retardant resin composition with above-mentioned composition; The transparency that can satisfy high flame retardancy and certain limit simultaneously is (in the thick profiled sheeting of 2mm; Total light transmittance is 74～87%); The resin combination that the space is big and outward appearance is excellent of comparing painted design with the PC of in the past interpolation fibrillation PTFE can be provided, have the characteristic that technology is not in the past had.
Embodiment
Below, illustrate in greater detail the present invention.
(A composition: aromatic polycarbonate resins)
The aromatic polycarbonate resins of using as the A composition in the present invention is that binary phenol and carbonic ether presoma are reacted and the resin that obtains.As the example of reaction method, can enumerate the solid phase ester-interchange method of interfacial polymerization, melt transesterification process, carbonic ether prepolymer and the ring-opening polymerization method of cyclic carbonate compound etc.
As representative example, can enumerate quinhydrones, Resorcinol, 4,4 '-bis-phenol, 1 at the binary phenol of this use; Two (4-hydroxy phenyl) ethane, 2 of 1-, two (4-hydroxy phenyl) propane of 2-(be referred to as dihydroxyphenyl propane usually, below abbreviate " BPA " sometimes as), 2; Two (the 4-hydroxy-3-methyl phenyl) propane, 2 of 2-, two (4-hydroxy phenyl) butane, 1 of 2-, two (4-the hydroxy phenyl)-1-diphenylphosphino ethanes, 1 of 1-; 1-bis(4-hydroxyphenyl) cyclohexane, 1; Two (the 4-hydroxy phenyls)-3,3 of 1-, 5-trimethyl-cyclohexane, 2; Two (4-hydroxy phenyl) pentanes, 4 of 2-; 4 '-(to the phenylene diisopropylidene) diphenol, 4,4 '-(metaphenylene diisopropylidene) diphenol, 1, two (4-the hydroxy phenyl)-4-normenthanes of 1-, two (4-hydroxy phenyl) oxide compound, two (4-hydroxy phenyl) sulfide, two (4-hydroxy phenyl) sulfoxide, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) ketone, two (4-hydroxy phenyl) ester, two (4-hydroxy-3-methyl phenyl) sulfide, 9; Two (4-hydroxy phenyl) fluorenes and 9 of 9-, two (4-hydroxy-3-methyl phenyl) fluorenes of 9-etc.Preferred binary phenol is two (4-hydroxy phenyl) paraffinic hydrocarbonss, wherein, considers from the shock-resistance aspect, and preferred especially dihydroxyphenyl propane is widely used.
In the present invention, except dihydroxyphenyl propane class polycarbonate, can also use the special polycarbonate of making through other binary phenol as the A composition as general polycarbonate.
For example, as the part of binary phenol composition or all, use 4; 4 '-(metaphenylene diisopropylidene) diphenol (following abbreviate as sometimes " BPM "), 1; 1-bis(4-hydroxyphenyl) cyclohexane, 1, two (the 4-hydroxy phenyls)-3,3 of 1-; 5-trimethyl-cyclohexane (following abbreviate as sometimes " Bis-TMC "), 9; Two (4-hydroxy phenyl) fluorenes and 9 of 9-, the polycarbonate (homopolymer or multipolymer) of two (the 4-hydroxy-3-methyl phenyl) fluorenes (following abbreviate as sometimes " BCF ") of 9-, the dimensional change or the shape stability that are suitable for suction is caused require on the strict especially purposes.These binary phenol except BPA, preferred 5 moles of the binary phenol composition total amount that constitutes this polycarbonate of using are preferably 10 moles more than the % more than the % especially.
Especially, under the situation that requires to have high rigidity and better hydrolytic resistance, the A composition that especially preferably constitutes resin combination is the Copolycarbonate of following (1)～(3).
(1) in the binary phenol composition of this polycarbonate of formation of 100 moles of %; BPM is 20～80 moles of % (40～75 moles of % more preferably; Further be preferably 45～65 moles of %) and BCF be the Copolycarbonate of 20～80 moles of % (more preferably 25～60 moles of % further are preferably 35～55 moles of %);
(2) in the binary phenol composition of this polycarbonate of formation of 100 moles of %; BPA is 10～95 moles of % (50～90 moles of % more preferably; Further be preferably 60～85 moles of %) and BCF be the Copolycarbonate of 5～90 moles of % (more preferably 10～50 moles of % further are preferably 15～40 moles of %);
(3) in the binary phenol composition of this polycarbonate of formation of 100 moles of %; BPM is 20～80 moles of % (40～75 moles of % more preferably; Further be preferably 45～65 moles of %) and Bis-TMC be the Copolycarbonate of 20～80 moles of % (more preferably 25～60 moles of % further are preferably 35～55 moles of %).
These special polycarbonate both can use separately, also can two or morely suitably mix and use.In addition, also can these be mixed use with general bisphenol A polycarbonate.
About the method for manufacture and the characteristic of these special polycarbonate, for example in the flat 6-172508 communique of TOHKEMY, TOHKEMY flat 8-27370 communique, TOHKEMY 2001-55435 communique and TOHKEMY 2002-117580 communique etc., detailed record is arranged.
In addition; In above-mentioned various polycarbonate; Through adjustment multipolymer composition etc. water-intake rate and Tg (second-order transition temperature) are adjusted at the polycarbonate in the following ranges, the hydrolytic resistance of its polymkeric substance self is good, and the low toughness after the moulding is also excellent especially; Therefore, be particularly suitable for requiring to have in the field of shape stability.
(i) water-intake rate is 0.05～0.15%, is preferably 0.06～0.13%; And Tg is 120～180 ℃ a polycarbonate; Perhaps
(ii) Tg is 160～250 ℃, is preferably 170～230 ℃; And water-intake rate is 0.10～0.30%, be preferably 0.13～0.30%, more preferably 0.14～0.27% polycarbonate.
At this, the water-intake rate of polycarbonate is to utilize diameter for 45mm, the thickness discoideus test piece for 3.0mm, according to ISO62-1980, is determined at moisture content and the numerical value that obtains after 24 hours of dipping in 23 ℃ the water.In addition, Tg (second-order transition temperature) is according to JIS K7121, the numerical value of trying to achieve with DSC (DSC) mensuration.
As the carbonic ether precursor, use carboxylic acid halides (Carbonyl halide), carbonic diester or haloformate (Ha ロ ホ Le メ one ト) etc., specifically, can enumerate the bishaloformate of phosgene (Phosgene), diphenyl carbonate or binary phenol etc.
When through interfacial polymerization, when making aromatic polycarbonate resin, also can use catalyzer, end to stop agent, inhibitor etc. as required by above-mentioned binary phenol and carbonic ether precursor, wherein inhibitor is in order to prevent the oxidation of binary phenol.In addition, the aromatic polycarbonate resin comprises: with the branched polycarbonate resin of copolymerization in addition of the multifunctional aromatics more than the three-functionality-degree; With two functionality carboxylic acids of aromatic series or aliphatics (comprising ester ring type) the polyestercarbonate resin of copolymerization in addition; With two functionality alcohol (the comprising ester ring type) copolymerized panlite of copolymerization in addition; And with this two functionality carboxylic acid and the two official's degree alcohol polyestercarbonate resin of copolymerization in addition.In addition, also can be two or more blended mixtures in addition with resulting aromatic polycarbonate resin.
Branched polycarbonate resin can be given antidrip drop etc. to resin combination of the present invention.As the multifunctional aromatics more than the three-functionality-degree that is used for this branched polycarbonate resin, can enumerate Phloroglucinol monomethyl ether, Gen Pi Portugal phenol or 4,6-dimethyl--2,4; 6-three (4-hydroxy phenyl) heptene-2,2,4,6-trimethylammonium-2,4; 6-three (4-hydroxy phenyl) heptane, 1,3,5-three (4-hydroxy phenyl) benzene, 1,1; 1-three (4-hydroxy phenyl) ethane, 1,1,1-three (3,5-dimethyl--4-hydroxy phenyl) ethane, 2; Two (2-hydroxy-5-methyl base the benzyl)-4-methylphenols of 6-, 4-{4-[1, two (4-hydroxy phenyl) ethyls of 1-] benzene }-α, the triphenol of α-Er Jiajibianji phenol etc.; Four (4-hydroxy phenyl) methane, two (2; The 4-dihydroxy phenyl) ketone, 1; Two (4, the 4-dihydroxyl trityl group) benzene of 4-or trimellitic acid, Pyromellitic Acid, benzophenone tetracarboxylic acid (Benzophenone tetracarboxylic) and their sour muriate etc.Wherein, preferred 1,1,1-three (4-hydroxy phenyl) ethane, 1,1,1-three (3,5-dimethyl--4-hydroxy phenyl) ethane is preferably 1,1,1-three (4-hydroxy phenyl) ethane especially.
100 moles of % from binary phenol deutero-structural unit with from the total amount of this polyfunctionality aromatics deutero-structural unit; In the preferred branched polycarbonate is 0.01～1 mole of % from polyfunctionality aromatics deutero-structural unit, is preferably 0.05～0.9 mole of %, is preferably 0.05～0.8 mole of % especially.
In addition; When particularly adopting melt transesterification process; Sometimes produce the branched structure unit as side reaction; About the unitary content of this branched structure, also from the total amount of binary phenol deutero-structural unit, accounting for 0.001～1 mole of %, be preferably 0.005～0.9 mole of %, be preferably 0.01～0.8 mole of % especially at 100 moles of %.In addition, the content of above-mentioned branched structure can pass through 1H-NMR measures and calculates.
Two functionality carboxylic acids of aliphatic are alpha, omega-dicarboxylic acid.As aliphatic two functionality carboxylic acids, preferably can enumerate direct-connected saturated aliphatic dicarboxylic acids such as sebacic acid (sebacic acid), dodecanedioic acid (Dodecandioic acid), tetradecane diacid, octadecane diacid, octadecane dicarboxylic acid; And the alicyclic dicarboxylic acid of cyclohexane dicarboxylic acid etc.As two functionality alcohol, be preferably alicyclic diol, for example can enumerate cyclohexanedimethanol, cyclohexane diol and tristane dimethanol etc.
In addition, can also use the polyorganosiloxane units polycarbonate-poly organo alkyl copolymer of copolymerization in addition.
As the reactive modes such as ring-opening polymerization method of interfacial polymerization, melt transesterification process, carbonic ether prepolymer solid phase ester-interchange method and the cyclic polycarbonates compound of the method for manufacture of polycarbonate resin of the present invention, be through known method such as various documents and patent gazette etc.
When making flame retardant resin composition of the present invention, the viscosity-average molecular weight (M) of aromatic polycarbonate resin is not done special qualification, but be preferably 1 * 10 4～5 * 10 4, more preferably 1.4 * 10 4～3 * 10 4, further be preferably 1.4 * 10 4～2.4 * 10 4
Be lower than 1.0 * 10 in viscosity-average molecular weight 4Aromatic polycarbonate resin in, can't obtain the favorable mechanical characteristic.On the other hand, surpass 5 * 10 by viscosity-average molecular weight 4The resin combination that obtains of aromatic polycarbonate resin, its flowability when injection molding is poor, so versatility is poor.
In addition, aromatic polycarbonate resin also can obtain through viscosity-average molecular weight is mixed at the aromatic polycarbonate resin beyond the above-mentioned scope.Particularly, has the above-mentioned scope (5 * 10 of surpassing 4) the aromatic polycarbonate resin of viscosity-average molecular weight, can improve the entropy-elasticity (entropyelasticity) of resin.Its result in the gas assistant formation and foaming that when reinforced resin material is shaped to structure unit, adopts, can bring into play good forming process property.This moment, the improvement of forming process property was more excellent than above-mentioned branched polycarbonate.As more preferred form, also can use the A composition is 7 * 10 by viscosity-average molecular weight 4～3 * 10 5Aromatic polycarbonate resin (A-1-1 composition) and viscosity-average molecular weight be 1 * 10 4～3 * 10 4Aromatic polycarbonate resin (A-1-2 composition) form, its viscosity-average molecular weight is 1.6 * 10 4～3.5 * 10 4Aromatic polycarbonate resin (A-1 composition) (below, be also referred to as " aromatic polycarbonate resin of pbz polymer amount composition " sometimes).
In the aromatic polycarbonate resin (A-1 composition) of above-mentioned pbz polymer amount composition, the molecular weight of preferred A-1-1 composition is 7 * 10 4～2 * 10 5, more preferably 8 * 10 4～2 * 10 5, further be preferably 1 * 10 5～2 * 10 5, be preferably 1 * 10 especially 5～1.6 * 10 5In addition, the molecular weight of A-1-2 composition is preferably 1.0 * 10 4～2.5 * 10 4, more preferably 1.1 * 10 4～2.4 * 10 4, further be preferably 1.2 * 10 4～2.4 * 10 4, be preferably 1.2 * 10 especially 4～2.3 * 10 4
The aromatic polycarbonate resin of pbz polymer amount composition (A-1 composition) can be through mixing above-mentioned A-1-1 composition and A-1-2 composition with various ratios, and it is adjusted into the molecular weight ranges that satisfies regulation and obtains.In the A-1 composition of 100 weight %, preferred A-1-1 composition is 2～40 weight %, 3～30 weight % more preferably, further is preferably 4～20 weight %, is preferably 5～20 weight % especially.
In addition, as the preparation method of A-1 composition, can enumerate, (1) is polymerization A-1-1 composition and A-1-2 composition independently respectively, and with they method of mixing in addition; (2) adopting with method shown in the flat 5-306336 communique of TOHKEMY is method representative, that will in same system, make according to the aromatic polycarbonate resin of a plurality of polymkeric substance peak values of expression in the graph of molecular weight distribution of GPC method, and makes this aromatic polycarbonate resin manufacture the method for the condition that satisfies A-1 composition of the present invention: and the A-1-1 composition of (3) aromatic polycarbonate resin that will obtain through this method of manufacture (method of manufacture of (2)) and manufacturing separately and/or A-1-2 composition method of mixing etc. in addition.
The said viscosity-average molecular weight of the present invention can be calculated according to following method.At first, from the solution that under 20 ℃, the 0.7g aromatic copolycarbonate is dissolved in the 100ml methylene dichloride and obtains, use Ostwald viscometer, obtain specific viscosity (η through following formula Sp):
Specific viscosity (η Sp)=(t-t 0)/t 0
[t 0Be drippage number second of methylene dichloride, drippage number second that t is sample solution];
According to resulting specific viscosity (η Sp), calculate viscosity-average molecular weight M through following formula:
η Sp/ c=[η]+0.45 * [η] 2C ([η] is limiting viscosity)
[η]＝1.23×10 -4M 0.83
c＝0.7。
In addition, in the flame retardant resin composition of the present invention, the calculating of the viscosity-average molecular weight of aromatic polycarbonate resin is to carry out according to following method.That is, this resin combination is mixed with 20～30 times methylene dichloride of its weight, thus the solvable composition in the dissolved composition.Obtain this solvable composition through diatomite filtration.Then, the solvent in the removal gained solution.Solid to behind the removal solvent carries out sufficient drying, obtains being dissolved in the solids component of methylene dichloride.The solution that obtains from this solid of 0.7g is dissolved in the 100ml methylene dichloride, obtain the specific viscosity under 20 ℃ with above-mentioned same operation, and, obtain viscosity-average molecular weight M with above-mentioned same operation from this specific viscosity.
(B composition: have the tetrafluoroethylene (fibrillation PTFE) that fibrillation forms function)
The fibrillation PTFE that uses among the present invention both can be independent fibrillation PTFE, also can be the fibrillation PTFE of mixed style,, also can be the tetrafluoroethylene class mixture of fibrillation PTFE particle and organic polymer formation that is.
Fibrillation PTFE has ultra high molecular weight, demonstrates external action through shearing force etc. and makes and combine to form fibrous tendency between the PTFE.Its number-average molecular weight is 1,500,000～several scopes of ten million.The lower limit of this number-average molecular weight more preferably 3,000,000.Shown in the flat 6-145520 communique of TOHKEMY, this number-average molecular weight can be calculated according to the melt viscosity of the tetrafluoroethylene under 380 ℃.That is, as the fibrillation PTFE of B composition, the melt viscosity under its 380 ℃ of measuring through the method put down in writing in this communique is 10 7～10 13The scope of poise is preferably 10 8～10 12The scope of poise.
This PTFE both can use the PTFE of solid shape, also can use the PTFE of aqueous liquid dispersion form.In addition, in order to improve the dispersiveness of fibrillation PTFE in resin, and in order to obtain more excellent flame and mechanical characteristics, also can use the PTFE mixture of mixed style of mixed with resin with other.In addition, also preferred utilization is put down in the 6-145520 communique disclosed like TOHKEMY, has with this fibrillation PTFE to be nuclear, to be the material of the structure of shell with low-molecular-weight tetrafluoroethylene.
As the commercially available article of this fibrillation PTFE, for example can enumerate DU PONT-MITSUIFLUOROCHEMICALS COMPANY, the Port リ Off ロ Application MPA FA500 that テ Off ロ Application (registered trademark) 6J of LTD, DAIKIN chemical industry (strain) are made, F-201L etc.Commercially available article as the aqueous liquid dispersion of fibrillation PTFE; For example can enumerate Off Le オ Application AD-1, AD-936 that rising sun ア イ シ one ア イ Off ロ ロ Port リ マ one ズ (strain) makes; Off Le オ Application D-1, D-2 that DAIKIN industry (strain) is made; DU PONT-MITSUI FLUOROCHEMICALSCOMPANY, テ Off ロ Application (registered trademark) 30J that LTD makes etc.
As the fibrillation PTFE of mixed style, can use the fibrillation PTFE of the mixed style that makes through the method shown in following (1)～(5).That is, (1) is with the aqueous liquid dispersion of the aqueous liquid dispersion of fibrillation PTFE and organic polymer or solution mixes and carry out co-precipitation and obtain the method (method of record in the clear 60-258263 communique of TOHKEMY, the clear 63-154744 communique of TOHKEMY etc.) of common aggegation mixture; (2) with the aqueous liquid dispersion of fibrillation PTFE and exsiccant organic polymer particle method of mixing (method of putting down in writing in the flat 4-272957 communique of TOHKEMY) in addition; (3) with aqueous liquid dispersion and the organic polymer particle solution uniform mixing of fibrillation PTFE, the method (TOHKEMY is equalled the method for putting down in writing 06-220210 communique, the flat 08-188653 communique of TOHKEMY etc.) of removing medium separately simultaneously from this mixture; (4) polymerization is used to form the monomer methods (method of putting down in writing in the flat 9-95583 communique of TOHKEMY) of organic polymer in the aqueous liquid dispersion of fibrillation PTFE; (5) behind the aqueous liquid dispersion and organic polymer dispersion liquid uniform mixing with PTFE, further polymerising ethylene class monomer in this mixed dispersion liquid obtains the method (methods of record in the flat 11-29679 communique of TOHKEMY etc.) of mixture then.
As the commercially available article of the fibrillation PTFE of these mixed styles, can enumerate [メ タ Block レ Application A3000] (trade(brand)name), [メ タ Block レ Application A3700] (trade(brand)name) made with Mitsubishi RayonCo.Ltd., メ タ Block レ Application A that [メ タ Block レ Application A3800] (trade(brand)name) be representative is serial; The POLY TS AD001 (trade(brand)name) of PIC society; And [BLENDEX B449] (trade(brand)name) of the manufacturing of GE ス ペ シ ヤ リ テ イ one ケ ミ カ Le ズ society etc.
As the ratio of the fibrillation PTFE of mixed style, in this mixture of 100 weight %, preferred fibrillation PTFE is 1～95 weight %, and more preferably 10～90 weight % further are preferably 20～80 weight %.When less than 1 weight %, the organic polymer part shared ratio in flame-retardant copolycarbonate resin of the present invention in the mixed style has the trend that becomes many, thereby transparent easy the reduction, and the effect of improving of flame retardant resistance also becomes beyond expression of words.When surpassing 95 weight %, then be difficult to reach high-caliber appearance.In addition, when surpassing 90 weight %, diminish, thereby aspect cost, considering to use is not that the fibrillation PTFE of mixed style is then more favourable with the difference of performance that is not the PTFE of mixed style.
The ratio of fibrillation PTFE in the mixed style can realize the good dispersiveness of fibrillation PTFE when this scope.
With respect to the A composition of 100 weight parts, the content of tetrafluoroethylene (B composition) in resin combination with fibril formation ability is preferably 0.1～0.2 weight part, and more preferably 0.1～0.19 weight part further is preferably 0.1～0.18 weight part.In addition, when tetrafluoroethylene of the present invention was mixed style (mixture), the weight part shown in was here represented the weight that mixture is whole.
A composition with respect to 100 weight parts; If the content with tetrafluoroethylene (B composition) of fibril formation ability departs from the scope of 0.1～0.2 weight part, then exist the problem of " the unique mist transparent feel " that can not only be expressed the transparent degree of stipulating in the resin combination of the present invention.In addition, when being lower than 0.10 weight part, can not keep sufficient flame retardant resistance, when surpassing 0.20 weight part, then exist the problem, the particularly shock strength in the test film of specific high-temperature area moulding that the mechanical-physical character of shock strength etc. reduces and reduce.
(C composition: fire retardant)
The fire retardant of C composition is as the fire retardant of polycarbonate resin and known various compound.The cooperation of this compound can bring the raising of flame retardant resistance, in addition, can also be based on the character of each compound, bring raising of for example static electricity resistance, flowability, rigidity and thermostability etc.As above-mentioned fire retardant, can enumerate (i) organic metal salt based flame retardant (for example, organic sulfonic acid alkali (alkali earths) metal-salt, organic boronic metallic salt fire retardant and organotin acid metal salt based flame retardant etc.); (ii) organic phosphates fire retardant (phosplate compound, SULPHOSUCCINIC ACID ESTER oligopolymer, phosphonate oligomers, phosphine nitrile oligopolymer and the phosphonic acid amide compound etc. that for example, contain organic group); The silicon based flame retardant that (iii) forms by silicon compound, wherein, preferred organic metallic salt fire retardant.
(i) organic metal salt based flame retardant
Organic metal salt fire retardant among the present invention is that carbonatoms is 1～50, is preferably 1～40 organic acid alkali (alkali earths) metal-salt, more preferably organic sulfonic acid alkali (alkali earths) metal-salt.This organic sulfonic acid alkali (alkali earths) metal-salt comprises: the metal-salt of fluorine substituted alkyl sulfonic acid is 1～10, is preferably 2～8 the perfluoro alkyl sulfonic acid and the metal-salt of basic metal or alkaline-earth metal like carbonatoms; And carbonatoms is 7～50, is preferably 7～40 the aromatic sulphonic acid and the metal-salt of basic metal or alkaline-earth metal.
As the basic metal that constitutes metal-salt of the present invention, can enumerate lithium, sodium, potassium, rubidium and caesium; As alkaline-earth metal, can enumerate beryllium, magnesium, calcium, strontium and barium.Basic metal more preferably.In this basic metal, but then, owing to they are not general and are difficult to make with extra care, therefore, there is defective in preferred bigger rubidium and the caesium of ionic radius that use on cost under the higher situation of the requirement of the transparency.In addition, the metal that lithium and sodium plasma radius are littler is then unfavorable to flame retardant resistance sometimes.Can use the basic metal in the sulfonic acid alkali metal salts according to above-mentioned situation difference, but no matter consider which aspect, the sulfonic acid potassium salt that balance of properties is excellent is best suited for all using.Also can be with this sylvite and sulfonic acid alkali metal salts that forms by other basic metal and usefulness.
As the object lesson of the fluorine-containing organic metal salt based flame retardant of perfluoro alkyl sulfonic acid an alkali metal salt etc., can enumerate trifluoromethayl sulfonic acid potassium, potassium perfluorobutane sulfonate, PFH potassium sulfonate, PFOS potassium, pentafluoride ethane sodium sulfonate, perfluorinated butane sodium sulfonate, PFOS sodium, trifluoromethayl sulfonic acid lithium, perfluorinated butane sulfonic acid lithium, PF 5070 sulfonic acid lithium, trifluoromethayl sulfonic acid caesium, perfluorinated butane sulfonic acid caesium, PFOS caesium, PFH sulfonic acid caesium, perfluorinated butane sulfonic acid rubidium and PFH sulfonic acid rubidium etc.These both can use a kind of separately, also can two or more and usefulness.At this, the carbonatoms of perfluoroalkyl be preferably 1～18 scope, more preferably 1～10 scope, further be preferably 1～8 scope.Wherein, be preferably potassium perfluorobutane sulfonate especially.
In perfluoro alkyl sulfonic acid alkali (alkali earths) metal-salt that forms by basic metal, sneak into a lot of fluoride ion (F usually -).Having of this fluoride ion possibly become the reason that reduces flame retardant resistance, therefore, preferably reduces the existence of fluoride ion as far as possible.The content of this fluoride ion can be measured through ion chromatography.Preferred fluorinated thing ionic content is below the 100ppm, more preferably below the 40ppm, be preferably below the 10ppm especially.In addition, when considering, more than the preferred 0.2ppm from making efficient.Reduced perfluoro alkyl sulfonic acid alkali (alkali earths) metal-salt of above-mentioned fluoride ion content, its method of manufacture adopts known method of manufacture, and can make through following method.That is the method etc. that the method for the fluoride ion content that contains in the raw material when, reduce making fluorine-containing organic metal salt, the gas that produces during with reaction or heating remove through the method for reacting resulting hydrogen fluoride etc. and reduce fluoride ion content when making fluorine-containing organic metal salt with the process for purification of recrystallization and redeposition etc.Particularly, because the C composition relatively dissolves easily in water, therefore, especially preferably make through following operation.This operation is, adopts ion exchanged water, and particularly adopting resistance value is more than the 18M Ω cm, and promptly electric conductivity satisfies the water that is about below the 0.55 μ S/cm, and under the temperature higher than normal temperature, dissolves and wash, and cools off the operation that makes it recrystallization then.
Object lesson as aromatic sulphonic acid alkali (alkali earths) metal-salt; For example; Can enumerate diphenyl sulfide-4; 4 '-disulfonic acid disodium, diphenyl sulfide-4; 4 '-disulfonic acid dipotassium, 5-sulfo group m-phthalic acid potassium, 5-sulfo group m-phthalic acid sodium, the many sodium of the many sulfonic acid of Vilaterm terephthalic acid (Port リ エ チ レ Application テ レ Off タ Le acid Port リ ス Le ホ Application acid Port リ Na ト リ ウ system), 1-methoxynaphthalene-4-calcium sulphonate, 4-lauryl phenyl ether disulfonic acid disodium, gather (2,6-dimethyl-phenylene oxide) many sodium of many sulfonic acid (Port リ (2,6 one ジ メ チ Le Off エ ニ レ Application オ キ シ De) Port リ ス Le ホ Application acid Port リ Na ト リ ウ system), gather (1; The 3-phenylene oxide) the many sodium of many sulfonic acid (Port リ (1; 3-Off エ ニ レ Application オ キ シ De) Port リ ス Le ホ Application acid Port リ Na ト リ ウ system), gather (1, the 4-phenylene oxide) many sodium of many sulfonic acid (Port リ (1,4-Off エ ニ レ Application オ キ シ De) Port リ ス Le ホ Application acid Port リ Na ト リ ウ system), gather (2; 6-phenylbenzene phenylene oxide) the many potassium of many sulfonic acid (Port リ (2; 6-ジ Off エ ニ Le Off エ ニ レ Application オ キ シ De) Port リ ス Le ホ Application acid Port リ カ リ ウ system), gather potassium sulfonate that (2-fluoro-6-butyl phenylene oxide) gather sulfonic acid lithium, benzene sulfonate, Supragil GN, Phenylsulfonic acid strontium, Phenylsulfonic acid magnesium, to benzene disulfonic acid dipotassium, naphthalene-2,6-disulfonic acid dipotassium, biphenyl-3,3 '-disulfonic acid calcium, sulfobenzide-3-sodium sulfonate, sulfobenzide-3-potassium sulfonate, sulfobenzide-3; 3 '-disulfonic acid dipotassium, sulfobenzide-3; 4 '-disulfonic acid dipotassium, α, α, α-trifluoroacetophenone-4-sodium sulfonate, UVNUL MS-40-3; 3 '-disulfonic acid dipotassium, thiophene-2; 5-disulfonic acid disodium, thiophene-2,5-disulfonic acid dipotassium, thiophene-2, the Superlysoform condenses of 5-disulfonic acid calcium, thionaphthene sodium sulfonate, diphenyl sulfoxide-4-potassium sulfonate, sodium naphthalene sulfonate and the Superlysoform condenses of anthracene sulfonic acid sodium etc.In these aromatic sulphonic acid alkali (alkali earths) metal-salts, preferred especially sylvite.
In these aromatic sulphonic acid alkali (alkali earths) metal-salts, preferred sulfobenzide-3-potassium sulfonate and sulfobenzide-3,3 '-disulfonic acid dipotassium, preferred especially their mixture (the former and the latter's weight ratio is 15/85～30/70).
As the organic metal salt beyond azochlorosulfonate acid alkali (alkali earths) metal-salt, can preferably enumerate alkali (alkali earths) metal-salt of sulfuric ester and alkali (alkali earths) metal-salt of aromatic sulfonamide etc.Alkali (alkali earths) metal-salt as sulfuric ester; Can enumerate alkali (alkali earths) metal-salt of monobasic and/or polyalcohols sulfuric ester especially; As this monobasic and/or polyalcohols sulfuric ester, can enumerate one, two, three, four sulfuric esters of methyl sulfate, sulfovinic acid, lauryl sulfate, hexadecyl hydrosulfate ester, the sulfuric ester that gathers hydroxyalkyl vinyl base alkyl phenyl ether, tetramethylolmethane, sulfuric ester, the sulfuric ester of hexadecanoic acid direactive glyceride and the sulfuric ester of glyceryl monostearate etc. of month silicic acid direactive glyceride.As alkali (alkali earths) metal-salt of these sulfuric esters, preferably enumerate alkali (alkali earths) metal-salt of lauryl sulfate.
As alkali (alkali earths) metal-salt of aromatic sulfonamide, for example can enumerate alkali (alkali earths) metal-salt of asccharin, N-p-toluenesulfonyl-tolysulfonyl imines, N-(N '-benzylamino carbonyl) sulfimide and N-(phenyl carboxyl) sulfimide etc.
With respect to the A composition of 100 weight parts, the content of organic metal salt based flame retardant is 0.001～1 weight part, be preferably 0.005～0.5 weight part, 0.01～0.3 weight part more preferably, further is preferably 0.03～0.15 weight part.
(ii) organic phosphates fire retardant
As the organic phosphates fire retardant, the preferred aryl groups phosphate compound.This is because all very excellent cause of the common color and luster of this phosphate compound.In addition, phosphate compound has the plasticity-effect, and is therefore, favourable aspect the forming process property that improves resin combination of the present invention.As this phosphate compound,, more preferably enumerate one or more the phosphate compound of particularly using formula (i) expression though can use in the past as the known various phosphate compounds of fire retardant.
Figure BSA00000614743900131
(in the formula (i), X 1For from binary phenol deutero-divalent organic group; R 1, R 2, R 3And R 4Distinguish independence and expression from monobasic phenol deutero-any monovalent organic radical group; J, k, l and m are independent respectively and be 0 or 1; N is 0～5 integer, and under the situation that is the different phosphate mixture of the polymerization degree, n representes its MV, is 0～5 numerical value.)
The phosphate compound of above-mentioned formula; It also can be mixture with compound of different n numerical value; When being this mixture, the MV of preferred n is 0.5～1.5, more preferably 0.8～1.2, further be preferably 0.95～1.15, be preferably 1～1.14 scope especially.
As the above-mentioned X that derives 1The preferred object lesson of binary phenol; Can enumerate by quinhydrones, Resorcinol, two (4-hydroxy diphenyl) methane, dihydroxyphenyl propane, dihydroxyl phenylbenzene, remove two hydroxyls in the dihydroxy compound of selecting among the crowd that dihydroxy naphthlene, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) ketone and two (4-hydroxy phenyl) sulfide are formed and the divalent group that obtains.
As R 1, R 2, R 3And R 4Object lesson, can enumerate respectively independent and can be substituted by more than one halogen atom, a hydroxyl of removal and the univalent perssad that obtains in the monohydroxy compound selected among the crowd that forms by phenol, cresols, xylenol, isopropyl-phenol, butylphenol and to cumyl phenol.
As the above-mentioned R that derives 1, R 2, R 3And R 4The preferred object lesson of a bivalent phenol, can enumerate phenol, cresols, xylenol, isopropyl-phenol, butylphenol and, wherein, be preferably phenol and 2, the 6-xylenol cumyl phenol.
In addition, this monobasic phenol can be replaced by halogen atom, as the object lesson that contains by the phosphate compound of this monobasic phenol deutero-group; Can enumerate three (2; 4,6-tribromo phenyl) SULPHOSUCCINIC ACID ESTER, three (2, the 4-bromophenyl) SULPHOSUCCINIC ACID ESTERs and three (4-bromophenyl) SULPHOSUCCINIC ACID ESTER etc.
On the other hand, as not by the object lesson of the substituted phosphate compound of halogen atom, can preferably enumerate phosplate compounds such as triphenyl and three (2, the 6-3,5-dimethylphenyl) SULPHOSUCCINIC ACID ESTER; And two two (2, the 6-3,5-dimethylphenyl) SULPHOSUCCINIC ACID ESTERs of Resorcinol are as the SULPHOSUCCINIC ACID ESTER oligopolymer of main body; With 4,4-dihydroxyl phenylbenzene two (diphenyl phosphoester) is as the SULPHOSUCCINIC ACID ESTER oligopolymer of main body; And with dihydroxyphenyl propane two (diphenyl phosphoesters) as main body the SULPHOSUCCINIC ACID ESTER oligopolymer (said as main body at this; Be that expression can contain other different compositions of the polymerization degree on a small quantity, preferably represent in the above-mentioned formula (1) component content of n=1 be 80 weight % above, more preferably 85 weight % above, further be preferably more than the 90 weight %.)
With respect to the A composition of 100 weight parts, the content of organic phosphates fire retardant is 0.01～20 weight part, be preferably 2～10 weight parts, 2～7 weight parts more preferably.
(iii) silicon based flame retardant
As the silicon compound that the silicon based flame retardant uses, the chemical reaction when being meant through burning improves the compound of flame retardant resistance.As this compound, all cpds that can use in the past the fire retardant as aromatic polycarbonate resin to propose.Silicon compound is considered to be in when burning, through himself combination or through combining to form structure (structure) with composition from resin, the reduction reaction during perhaps through this structure of formation is given flame retardant effect to polycarbonate resin.Therefore, preferably contain active high group in above-mentioned reaction.More particularly, preferably contain at least a group that is selected from alkoxyl group and the hydrogen base (Ha イ De ロ ヅ エ Application) (being the Si-H yl).The content of preferred this group (alkoxyl group, Si-H yl) than be the scope of 0.1～1.2mol/100g, more preferably 0.12～1mol/100g scope, further be preferably the scope of 0.15～0.6mol/100g.This content ratio, caustic leaching process capable of using is obtained through hydrogen or pure amount that the silicon compound of measuring per unit weight produces.In addition, preferred alkoxyl group is that carbonatoms is 1～4 alkoxyl group, is preferably methoxyl group especially.
Usually, the structure of silicon compound is to constitute through the following four kinds of siloxane units of arbitrary combination.That is,
M unit: (CH 3) 3SiO 1/2, H (CH 3) 2SiO 1/2, H 2(CH 3) SiO 1/2, (CH 3) 2(CH 2=CH) SiO 1/2, (CH 3) 2(C 6H 5) SiO 1/2, (CH 3) (C 6H 5) (CH 2=CH) SiO 1/2Deng the single functionality siloxane unit;
D unit: (CH 3) 2SiO, H (CH 3) SiO, H 2SiO, H (C 6H 5) SiO, (CH 3) (CH 2=CH) SiO, (C 6H 5) 2The two functionality siloxane units of SiO etc.;
T unit: (CH 3) SiO 3/2, (C 3H 7) SiO 3/2, HSiO 3/2, (CH 2=CH) SiO 3/2, (C 6H 5) SiO 3/2Deng the three-functionality-degree siloxane unit;
Q unit: use SiO 2Four functionality siloxane units of expression.
The structure that is used for the silicon compound of silicon based flame retardant can be enumerated the structure of representing with following signal formula particularly, that is, and and D n, T p, M mD n, M mT p, M mQ q, M mD nT p, M mD nQ q, M mT pQ q, M mD nT pQ q, D nT p, D nQ q, D nT pQ qWherein, preferred silicon compound structure is M mD n, M mT p, M mD nT p, M mD nQ q, preferred structure is M mD nOr M mD nT p
At this, the Coefficient m in the above-mentioned signal formula, n, p, q are the integer more than 1 of the polymerization degree of each siloxane unit of expression, and the summation of coefficient is the mean polymerisation degree of silicon compound in each signal formula.Preferred this mean polymerisation degree 3～150 scope, more preferably 3～80 scope, further be preferably 3～60 scope, be preferably 4～40 scope especially.This mean polymerisation degree is in preferred range more, and its flame retardant resistance is then more excellent.And, contain just like after the silicon compound of aromatic group of the specified amount stated, its transparency or color and luster are also excellent.Consequently, can access good reflected light.
In addition, when among m, n, p, the q any one is the numerical value more than 2,, can be that institute's bonded Wasserstoffatoms or organic residue are different two or more siloxane units with the siloxane unit of this coefficient.
Silicon compound both can be a linear chain structure, also can be the silicon compound with branched structure.In addition, being preferably carbonatoms with the organic residue of Siliciumatom bonded is organic residue of 1～30, more preferably 1～20.As this organic residue, can enumerate the alkyl of methyl, ethyl, propyl group, butyl, hexyl and decyl etc. particularly; The naphthenic base of cyclohexyl etc.; The aryl of phenyl etc.; The aralkyl of tolyl etc. etc.More preferably carbonatoms is 1～8 alkyl, thiazolinyl or aryl.As alkyl, the carbonatoms that is preferably methyl, ethyl, propyl group etc. especially is 1～4 alkyl.
And the silicon compound that uses as the silicon based flame retardant preferably contains aryl.On the other hand, silane compound and silicone compounds as organic surface treatment agent of TiO 2 pigment can access the ideal effect when it does not contain aryl, therefore, can be differentiated clearly in its preferred form with the silicon based flame retardant.Preferred silicon based flame retardant is that the ratio (aromatic group amount) of the aromatic group (ii) represented with formula is the silicon compound of 10～70 weight % (15～60 weight % more preferably).
Figure BSA00000614743900161
(formula (ii) in, X representes independently that respectively OH base, carbonatoms are 1～20 the organic residue of monovalence; N representes 0～5 integer.And formula (ii) in, when n is 2 when above, can get mutual different types of X respectively.)
The silicon compound that uses as the silicon based flame retardant except above-mentioned Si-H base and can also contain reactive group the alkoxyl group, as this reactive group, for example can be enumerated amino, carboxyl, epoxy group(ing), vinyl, sulfydryl, methacryloxy etc.
As silicon compound, preferably enumerate and contain useful formula (iii) and at least a above silicon compound in the structural unit of (iv) expression with Si-H base:
Figure BSA00000614743900162
Figure BSA00000614743900163
(formula (iii) and formula (iv) in, Z 1～Z 3Represent independently respectively Wasserstoffatoms, carbonatoms be 1～20 the organic residue of monovalence, or with the formula (compound of v) representing; α 1～α 3 representes 0 or 1 respectively independently; Ml representes the integer more than 0 or 1; Further, formula (iii) in, when ml is 2 when above, its repeating unit can be got different a plurality of repeating units each other respectively.)
Figure BSA00000614743900171
(formula (v), Z 4～Z 8Represent independently that respectively Wasserstoffatoms, carbonatoms are 1～20 the organic residue of monovalence; α 4～α 8 representes 0 or 1 respectively independently; M2 representes the integer more than 0 or 1; Further, (v), when m2 is 2 when above, its repeating unit can be got different a plurality of repeating units each other respectively in formula.)
At the silicon compound that is used for the silicon based flame retardant, as silicon compound with alkoxyl group, for example can enumerate be selected from general formula (vi) and general formula (vii) the expression compound at least a compound:
(formula (vi), β 1Expression vinyl, carbonatoms are that 1～6 alkyl, carbonatoms are that 3～6 naphthenic base, carbonatoms are 6～12 aryl and aralkyl; γ 1, γ 2, γ 3, γ 4, γ 5And γ 6The expression carbonatoms is that 1～6 alkyl and naphthenic base and carbonatoms are 6～12 aryl and aralkyl, and wherein at least one group is an aryl or aralkyl; δ 1, δ 2, δ 3The expression carbonatoms is 1～4 alkoxyl group.)
Figure BSA00000614743900181
(formula (vii), β 2, β 3Expression vinyl, carbonatoms are that 1～6 alkyl, carbonatoms are that 3～6 naphthenic base and carbonatoms are 6～12 aryl and aralkyl; γ 7, γ 8, γ 9, γ 10, γ 11, γ 12, γ 13And γ 14The expression carbonatoms is that 1～6 alkyl, carbonatoms are that 3～6 naphthenic base, carbonatoms are 6～12 aryl and aralkyl, and wherein at least one group is an aryl or aralkyl; δ 4, δ 5, δ 6, δ 7The expression carbonatoms is 1～4 alkoxyl group.)
With respect to the A composition of 100 weight parts, the content of silicon based flame retardant is 0.01～20 weight part, be preferably 0.5～10 weight part, 1～5 weight part more preferably.
(other composition)
Can cooperate the various additives that cooperate usually in a spot of reinforcement packing material, the polycarbonate resin in the flame-retardant polycarbonate resin composition of the present invention.
(I) strengthen packing material
Can cooperate at least a reinforcement packing material that is selected among the crowd who forms by tabular inorganic filling material and fibrous inorganic filling material as strengthening packing material.But,, therefore preferably adopt little silicate minerals class packing material of shape or category of glass packing material as strengthening packing material because resin combination of the present invention requires to have good surface appearance.As this silicate minerals class packing material, can preferably enumerate talcum, white mica, synthetic fluorine mica, smectite and wollastonite.As the category of glass packing material, can enumerate spun glass, sheet glass and glass milled fiber etc.Silicate minerals class packing material and category of glass packing material can adopt the packing material of coating of metal oxides such as its surperficial oxidized titanium, zinc oxide, cerium oxide and silicon oxide.
Above-mentioned reinforcement packing material can be implemented surface treatment by surface treatment agent in advance.As this surface treatment agent; Can enumerate the various surface treatment agents of silane coupling agent (comprise alkylalkoxy silane or gather organohydrogensiloxanes etc.), high-grade aliphatic ester, acid cpd (for example, phosphorous acid, phosphoric acid, carboxylic acid, carboxylic acid anhydride etc.) and wax etc.Further, also can carry out granulation and make it to become particulate state through the collecting agent of various resins, high-grade aliphatic ester and wax etc.
With respect to the A composition of 100 weight parts, the content of strengthening packing material is 1～50 weight part, be preferably 1～20 weight part, 1～3 weight part more preferably.
(II) Phosphorus stablizer
In the flame retardant resin composition of the present invention, can not promote preferably to cooperate Phosphorus stablizer in the extent and scope of hydrolysis.This Phosphorus stablizer can improve when making or the thermostability during forming process, and improves mechanical characteristics, color and luster and forming stability.As Phosphorus stablizer, can enumerate phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acids and these sour esters and tertiary phosphine etc.
As concrete phosphorous acid ester (phosphite) compound; Can enumerate; Triphenyl phosphite, three (nonyl phenyl) phosphorous acid ester, three decyl phosphorous acid esters, trioctylphosphine phosphorous acid ester, three (octadecyl) phosphorous acid ester, didecyl list phenyl phosphites, dioctyl list phenyl phosphites, di-isopropyl list phenyl phosphites, monobutyl phenylbenzene phosphorous acid ester, single decyl phenylbenzene phosphorous acid ester, single octyl group phenylbenzene phosphorous acid ester, 2; 2-methylene-bis (4; The 6-di-tert-butyl-phenyl) octyl group phosphorous acid ester, three (diethylammonium phenyl) phosphorous acid ester, three (diisopropyl phenyl) phosphorous acid ester, three (di-n-butyl phenyl) phosphorous acid ester, three (2; The 4-di-tert-butyl-phenyl) phosphorous acid ester, three (2; The 6-di-tert-butyl-phenyl) phosphorous acid ester, distearyl pentaerythritol diphosphites, two (2; The 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2; 6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphites, phenyl dihydroxyphenyl propane pentaerythritol diphosphites, two (nonyl phenyl) pentaerythritol diphosphites, dicyclohexyl pentaerythritol diphosphites etc.
Further, as other bi-ester of phosphite, can use the bi-ester of phosphite that reacts and have ring texture with the binary phenol.For example, can enumerate 2,2 '-methylene-bis (4; The 6-di-tert-butyl-phenyl) (2; The 4-di-tert-butyl-phenyl) phosphorous acid ester, 2,2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) (the 2-tertiary butyl-4-aminomethyl phenyl) phosphorous acid ester, 2; 2 '-methylene-bis (4-methyl-6-tert butyl phenyl) (the 2-tertiary butyl-4-aminomethyl phenyl) phosphorous acid ester, 2,2 '-ethylenebis (4-methyl-6-tert butyl phenyl) (the 2-tertiary butyl-4-aminomethyl phenyl) phosphorous acid ester etc.
As SULPHOSUCCINIC ACID ESTER (phosphate) compound; Can enumerate tributyl phosphate, trimethyl phosphite 99, Tritolyl Phosphate, triphenylphosphate, trichlorophenyl SULPHOSUCCINIC ACID ESTER, triethyl phosphate, diphenylmethyl benzenephosphonic acid ester, the adjacent xenyl SULPHOSUCCINIC ACID ESTER of phenylbenzene list, three butoxyethyl group SULPHOSUCCINIC ACID ESTERs, dibutyl phosphate, dioctylphosphoric acid ester, diisopropyl phosphate etc., preferably phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite 99.
As phosphinate compound (phosphonite), can enumerate four (2, the 4-di-tert-butyl-phenyl)-4; 4 '-diphenylene, two phosphinates, four (2, the 4-di-tert-butyl-phenyl)-4,3 '-diphenylene, two phosphinates, four (2; The 4-di-tert-butyl-phenyl)-3,3 '-diphenylene, two phosphinates, four (2, the 6-di-tert-butyl-phenyl)-4; 4 '-diphenylene, two phosphinates, four (2, the 6-di-tert-butyl-phenyl)-4,3 '-diphenylene, two phosphinates, four (2; The 6-di-tert-butyl-phenyl)-3,3 '-diphenylene, two phosphinates, two (2, the 4-di-tert-butyl-phenyl)-4-phenyl-phenyl-phosphonite ester, two (2; The 4-di-tert-butyl-phenyl)-3-phenyl-phenyl-phosphonite ester, two (2; 6-di-n-butyl phenyl)-3-phenyl-phenyl-phosphonite ester, two (2, the 6-di-tert-butyl-phenyl)-4-phenyl-phenyl-phosphonite ester, two (2, the 6-di-tert-butyl-phenyl)-3-phenyl-phenyl-phosphonite esters etc.Wherein, Preferred four (di-tert-butyl-phenyl)-diphenylenes, two phosphinates, two (di-tert-butyl-phenyls)-phenyl-phenyl-phosphonite ester; More preferably four (2, the 4-di-tert-butyl-phenyl)-diphenylene two phosphinates, two (2, the 4-di-tert-butyl-phenyl)-phenyl-phenyl-phosphonite ester.This phosphinate compound can have the bi-ester of phosphite and the usefulness of two above substituted aryls with abovementioned alkyl, and preferably adopts this mode.
As phosphonate compound (phosphonate), can enumerate phosphenylic acid dimethyl ester, phosphenylic acid diethyl ester and phosphenylic acid dipropyl etc.
As tertiary phosphine, can enumerate triethyl phosphine, tripropyl phosphine, tributylphosphine, tri octyl phosphine, three amyl group phosphines, dimethylphenylphosphine, dibutyl Phenylphosphine, diphenyl methyl phosphine, phenylbenzene octyl group phosphine, triphenylphosphine, three pairs of toluene phosphines, three naphthyl phosphines and phenylbenzene benzyl phosphines etc.Preferred especially tertiary phosphine is a triphenylphosphine.
Above-mentioned Phosphorus stablizer both can use separately, also can two or more mixing use.In above-mentioned Phosphorus stablizer, preferably cooperating with the trimethyl phosphite 99 is the alkyl acid phosphate ester cpds of representative.In addition, also preferably with this alkyl acid phosphate ester cpds and bi-ester of phosphite and/or phosphinate compound and usefulness.
(III) Hinered phenols stablizer
In the flame retardant resin composition of the present invention, can also cooperate the Hinered phenols stablizer.Through cooperating this Hinered phenols stablizer, can bring into play that color and luster when for example suppressing forming process worsens or life-time service in the effect that worsens of color and luster.As the Hinered phenols stablizer, for example can enumerate alpha-tocopherol, butylhydroxy toluene, sinapyl alcohol, vitamin E, Octadecane base-β-(4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) propionic ester, the 2-tertiary butyl-6-(3 '-tertiary butyl-5 '-methyl 2 '-hydroxybenzyl)-4-aminomethyl phenyl propenoate, 2,6-di-t-butyl 4-(N; The N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids diethyl ester, 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 4; 4 '-methylene-bis (2,6 di t butyl phenol), 2,2 '-methylene-bis(4-methyl-6-cyclohexyl phenol), 2,2 '-methylene-bis (6-α-Jia Jibianji-p-cresol), 2; 2 '-ethylidene-two (4, the 6-DI-tert-butylphenol compounds), 2,2 '-butylidene-two (4-methyl-6-tert butyl phenol), 4,4 '-butylidene-two (3 methy 6 tert butyl phenol), triethylene glycol-N-be two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester, 1; 6-pinakon-two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], two [the 2-tertiary butyl-4-methyl-6-(the 3-tertiary butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3, two { 2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy]-1, the 1-dimethyl ethyls }-2 of 9-; 4,8,10-four oxaspiros [5,5] undecane, 4; 4 '-thiobis (the 6-tertiary butyl-meta-cresol), 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-thiobis (4-methyl-6-tert butyl phenol), two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) sulfide, 4; 4 '-dithio two (2,6 di t butyl phenol), 4,4 '-trithio two (2; The 6-DI-tert-butylphenol compounds), 2,2-sulfo-divinyl two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic esters], 2; Two (n-octyl the sulfo-)-6-(4-hydroxyl-3 ', 5 '-di-t-butyl phenylamino)-1,3 of 4-; 5-triazine, N, N '-hexa-methylene is two-(3,5-di-t-butyl-4-hydroxyl hydrocinnamamide), N; Two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl group] hydrazines, 1,1 of N-; 3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3,5-trimethylammonium-2; 4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, three (3; The 5-di-tert-butyl-hydroxy phenyl) chlorinated isocyanurates, three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) chlorinated isocyanurates, 1,3; 5-three (the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) chlorinated isocyanurates, 1,3; 5-32 [3 (3, the 5-di-tert-butyl-hydroxy phenyl) propionyloxy] ethyl chlorinated isocyanurates, four [methylene radical-3-(3 ', 5 '-di-tert-butyl-hydroxy phenyl) propionic ester] methane etc.These all are easy to obtain.Above-mentioned Hinered phenols stablizer both can use separately, also can two or more combinations use.
With respect to the A composition of 100 weight parts, the content of Phosphorus stablizer and Hinered phenols stablizer is 0.0001～1 weight part, be preferably 0.001～0.5 weight part, 0.005～0.3 weight part more preferably.
(IV) above-mentioned thermo-stabilizer in addition
In flame retardant resin composition of the present invention,, can also cooperate other thermo-stabilizer except above-mentioned Phosphorus stablizer and the Hinered phenols stablizer.As these other thermo-stabilizer, for example can preferably enumerate with 3-hydroxyl-5, the resultant of reaction of 7-di-t-butyl-furans-2-ketone and o-Xylol is the lactone stablizer of representative.About the detailed content of this stablizer, on the books in the flat 7-233160 communique of TOHKEMY.This compound is as Irganox HP-136 (trade mark, CIBA SPECIALTYCHEMICALS manufactured) and commercially available, this compound capable of using.In addition, commercially available in addition with this compound and various bi-ester of phosphite and hindered phenol compound blended stablizer in addition.For example, can enumerate the Irganox HP-2921 of above-mentioned company.With respect to the A composition of 100 weight parts, the content of preferred lactone stablizer is 0.0005～0.05 weight part, more preferably 0.001～0.03 weight part.
In addition, as other stablizers, can enumerate the sulphur-containing stabilizer of tetramethylolmethane four (3-mercaptopropionic acid ester), tetramethylolmethane four (3-lauryl thiopropionate) and USP Kosher-3-stearyl thiopropionate etc.With respect to the A composition of 100 weight parts, preferably the content of this sulphur-containing stabilizer is 0.001～0.1 weight part, more preferably 0.01～0.08 weight part.
(V) UV light absorber
In flame retardant resin composition of the present invention, can cooperate UV light absorber in order to give photostabilization.
As UV light absorber; Can enumerate benzophenone particularly; For example can enumerate 2; 4-dihydroxy benaophenonel, 2-hydroxyl-4-methoxy benzophenone, 2-hydroxyl-4-octyloxy UVNUL MS-40,2-hydroxyl-4-benzyloxy UVNUL MS-40,2-hydroxyl-4-methoxyl group-5-sulphur oxygen base UVNUL MS-40,2-hydroxyl-4-methoxyl group-5-sulphur oxygen base Trihydride UVNUL MS-40 (2-ヒ De ロ キ シ-4-メ ト キ シ-5-ス Le ホ キ シ ト リ Ha イ De ラ イ De レ イ ト ベ Application ゾ Off エ ノ Application), 2,2 '-dihydroxyl-4-methoxy benzophenone, 2,2 '; 4; 4 '-tetrahydroxybenzophenone, 2,2 '-dihydroxyl-4,4 '-dimethoxy-benzophenone, 2; 2 '-dihydroxyl-4,4 '-dimethoxy-5-sulphur oxygen acid sodium UVNUL MS-40, two (5-benzoyl-4-hydroxyl-2-p-methoxy-phenyl) methane, 2-hydroxyl-4-positive 12-alkoxy benzophenone and 2-hydroxyl-4-methoxyl group-2 '-carboxyl benzophenone etc.
Benzotriazole category as UV light absorber; Can enumerate 2-(2-hydroxy-5-methyl base phenyl) benzotriazole, 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole, 2-(2-hydroxyl-3 particularly; The 5-dicumylphenyl) phenyl benzotriazole, 2-(2-hydroxy-3-t-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2; [4-(1 for 2 '-methylene-bis; 1; 3,3-tetramethyl butyl)-6-(2H-benzotriazole-2-yl) phenol], 2-(2-hydroxyl-3,5-di-tert-butyl-phenyl) benzotriazole, 2-(2-hydroxyl-3; The 5-di-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2-hydroxyl-3; The 5-di-tert-pentyl-phenyl) benzotriazole, 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole, 2-(2-hydroxyl-5-tert-butyl-phenyl) benzotriazole, 2-(2-hydroxyl-4-octyloxyphenyl) benzotriazole, 2,2 '-methylene-bis (4-cumyl-6-benzotriazole phenyl), 2,2 '-TOPOT 2,2 (1; 3-benzoxazine-4-ketone), 2-[2-hydroxyl-3-(3; 4,5,6-tetrahydrochysene phthalic diamide methyl)-the 5-aminomethyl phenyl] benzotriazole, 2-(2 '-hydroxy-5-methyl base acrylyl oxy-ethyl phenyl)-2H-benzotriazole with can with the multipolymer of the vinyl monomer of this monomer copolymerizable or 2-(2 '-hydroxyl-5-acrylyl oxy-ethyl phenyl)-2H-benzotriazole with can be with the polymkeric substance with 2-hydroxy phenyl-2H-benzotriazole skeleton of the multipolymer of the vinyl monomer of this monomer copolymerizable etc. etc.
As the hydroxyphenyltriazinuv of UV light absorber, for example, can enumerate particularly 2-(4,6-phenylbenzene-1,3; 5-triazine-2-yl)-and 5-hexyl oxy phenol, 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-methyl oxy phenol, 2-(4,6-phenylbenzene-1; 3,5-triazine-2-yl)-and 5-ethyl oxy phenol, 2-(4,6-phenylbenzene-1,3; 5-triazine-2-yl)-5-propyl group oxy phenol and 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-butyl oxy phenol etc.Further, the phenyl that can also enumerate in 2-(4, two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines-2-yls of 6-)-above-mentioned example compound such as 5-hexyl oxy phenol becomes 2, the compound of 4-3,5-dimethylphenyl.
As the cyclic imide base ester of UV light absorber, for example can enumerate 2 particularly, 2 '-TOPOT 2,2 (3; 1-benzoxazine-4-ketone), 2,2 '-metaphenylene two (3,1-benzoxazine-4-ketone) and 2; 2 '-p, p '-diphenylene two (3,1-benzoxazine-4-ketone) etc.
In addition, as the cyanoacrylate of UV light absorber, for example can enumerate 1 particularly; 3-pair-[(2 '-cyanic acid-3 '; 3 '-diphenylprop enoyl-) oxygen]-2,2-pair-[(2-cyanic acid-3,3-diphenylprop enoyl-) oxygen] methylpropane and 1; 3-pair-[(2-cyanic acid-3,3-diphenylprop enoyl-) oxygen] benzene etc.
Further; Above-mentioned UV light absorber also can be; Through adopting the monomeric compound structure to carry out radical polymerization, the monomer of this ultraviolet-absorbing monomer and/or light stability monomer and (methyl) alkyl acrylate etc. is carried out copolymerization and the aggretion type UV light absorber that obtains.As above-mentioned UV light absorber monomer, can preferably enumerate the compound that contains benzotriazole skeleton, UVNUL MS-40 skeleton, triazine skeleton, cyclic imino ester skeleton and cyanoacrylate skeleton in the ester substituting group of (methyl) propenoate.
In above-mentioned, when considering ultraviolet absorption ability, preferably adopt benzotriazole category and hydroxyphenyltriazinuv class, and when considering thermotolerance and color and luster, then preferably adopt cyclic imino ester class and cyanoacrylate.Above-mentioned UV light absorber both can use separately, can also use two or more mixtures.
With respect to the A composition of 100 weight parts, the content of UV light absorber is 0.01～2 weight part, is preferably 0.02～2 weight part, and more preferably 0.03～1 weight part further is preferably 0.05～0.5 weight part.
(VI) other
Except above-mentioned, in order to give various functions to the moulding article or to improve characteristic, can also cooperate in the flame retardant resin composition of the present invention a spot of himself by known additive.These additives can cooperate according to common use level in the scope of not damaging the object of the invention.
As this additive, can enumerate antiseize paste (for example PTFE particle), tinting material (the for example pigment of carbon black, titanium oxide etc., dyestuff), light diffusing agent (for example vinylformic acid crosslinked particle, ZGK 5 crosslinked particle, calcium carbonate particles), optical dye, white dyes, photostabilizer (is representative with the hindered amine compound), mineral-type fluor (for example with the fluor of aluminate), static inhibitor, crystallization nucleating agent, inorganic or organic antibacterial agent, photocatalyst class stain control agent (for example micropartical titanium oxide, micropartical zinc oxide), releasing agent, mobile modification agent, free radical generating agent, infrared absorbent (hot line absorption agent) and photochromic agent etc. as the crystallization masterbatch.
< transparency of resin combination of the present invention >
Resin combination of the present invention, owing to contain fibrillation PTFE, though can not keep the original transparency of polycarbonate resin fully, but owing to the addition with fibrillation PTFE is limited in a spot of specified range, thereby have certain transparency.For example,, when measuring its total light transmittance, then be limited at 74.0%～87.0%, be preferably 75.0%～87.0%, more preferably 76.0%～87.0% scope by the thick profiled sheeting of resin combination moulding 2mm of the present invention.The transparency of this limited range promptly, produces unique " sending out the transparency of mist " high appearance property.And, comprise painted design space sensation, functional part and also have the wide space that is equal to mutually with polycarbonate resin material with original transparency.
In the situation of not using coloured material, resin combination of the present invention can create " a unique mist transparent feel " of only expressing the transparent degree of stipulating in the resin combination of the present invention.In addition, be the situation of coloured material using various dyestuffs, through suppressing its addition, pigmentable goes out the color of generation " a unique mist transparent feel ", can strengthen painted unique mist sense that suppresses through increasing addition.In addition, through with pigment be that coloured material combination is used, or to use pigment separately be coloured material, pigmentable becomes translucent colour or opaque colored, can keep very wide painted design space.In flame-retardant polycarbonate resin composition of the present invention; If the total light transmittance of the profiled sheeting that moulding 2mm is thick departs from 74.0%～87.0% scope; Then can not create " a unique mist transparent feel " of only expressing the transparent degree of stipulating in the resin combination of the present invention; In other words, can not create " unique send out mist transparent feel " who is limited to through addition that specific scope brings with fibrillation PTFE.
< about the method for manufacture of resin combination >
When making resin combination of the present invention, its method of manufacture is not done special qualification.But in order to realize the good dispersion of fibrillation PTFE or fibrillation PTFE class mixture (mixed style), the preferred method of manufacture of resin combination of the present invention is for adopting like the multiple screw extruder of biaxial extruder each composition method of melting mixing in addition.
As the representative example of biaxial extruder, can enumerate ZSK (trade(brand)name, Werner &Pfleiderer manufactured).As the object lesson of same model, can enumerate TEX (trade(brand)name, (strain) JSW makes), TEM (trade(brand)name, toshiba machine (strain) is made), KTX (trade(brand)name, the manufacturing of (strain) Kobe Steel) etc.In addition, as object lesson, can also enumerate the melting mixing machine of FCM (trade(brand)name, Farrel manufactured), Ko-Kneader (trade(brand)name, Buss manufactured) and DSM (trade(brand)name, Krauss-Maffei manufactured) etc.In above-mentioned, preferably be the model of representative with ZSK.In the biaxial extruder of this ZSK model, its screw rod is complete meshing type, and screw rod is made up of length various screw portions and the different various kneading disks (kneader disc) (or the mixing part of using suitable with it) of width different with spacing.
In biaxial extruder, preferred mode is for being described below.Promptly; The screw rod shape can adopt the screw-type screw rod (ネ ヅ ス Network リ ユ one) of single thread, double thread and triple thread, preferably especially uses the transporting power of molten resin or shears all wide double thread screw rod of the two aspect scope of applications of mixing ability.The ratio (L/D) of spiro rod length in the biaxial extruder (L) and diameter (D) is preferably 20～45, and more preferably 28～42.The L/D value is reached uniform dispersion state more greatly more easily, but when too big, is easy to generate the decomposition of resin because of thermal ageing.Screw rod must have more than one mixing district, preferably has 1～3, and wherein, said mixing district is by kneading disk part (perhaps suitable with it the mixing part) formation that is used to improve mixing property.
Further, as forcing machine, the preferred forcing machine that uses with the venting port that can remove the moisture in the raw material or the volatile gases that produces by the melting mixing resin.Preferably be provided with and be used for moisture that is produced or volatilization gas being drained into the outside vacuum pump of forcing machine effectively from venting port.In addition, the zone before forcing machine mould portion is provided with and is used to remove the filtering net of sneaking into extruding impurities in raw materials etc., also can impurity be removed from resin combination thus.As this filtering net, can enumerate wire netting, screen replacing device, sintered metal plates (disc filter etc.) etc.
And; To with C composition and other additives (in the following illustration; Only being called " additive ") method of supplying with forcing machine do not have special qualification, but can enumerate following method as its representational example: the method for (i) additive and polycarbonate resin being supplied with independently forcing machine respectively; (ii) adopt the mixing machine of super mixing machine etc.; After in advance additive and polycarbonate resin powder being carried out pre-mixing; Resupply the method for forcing machine and (iii) in advance additive and polycarbonate resin are carried out melting mixing, process the method for host grain (マ ス タ one ペ レ Star ト).
Aforesaid method one of (ii), for needed starting material all being carried out resupply after the pre-mixing method of forcing machine.Other method is the host (マ ス タ one drug) that is combined with additive with processing high density earlier, this host is further carried out pre-mixing individually or with remaining polycarbonate resin after, resupply the method for forcing machine.In addition, this host can be selected random shape Powdered and that this powder compressed granulation etc.In addition,, for example can enumerate Nautamixer, V-type mixing tank, Henschel mixing tank, chemomotive force device and extrude mixing tank etc. as other pre-blend approach, but the mixing tank of the high-speed stirring type of preferred super mixing tank etc.Further, other pre-blend approach for example is that polycarbonate resin and additive are dispersed in solvent and behind the obtain solution, remove the method for this solvent.
Through the resin that forcing machine is extruded, can directly cut off and carry out prilling, or after forming strand, this strand is cut off with tablets press and carries out prilling.In addition, outside during when being necessary to reduce like the influencing of dust etc., preferably the environmental gas around the forcing machine carry out cleaningization.Further; In this particulate is made; Can be through the whole bag of tricks that has proposed in polycarbonate resin at CD, suitably carry out the minimizing of minimizing and strand or the bubble (bubbles of vacuum) that granule interior produces of narrow and smallization that particle shape distributes, the short small powder of cutting minimizing, the transportation of thing (ミ ス カ Star ト thing) or producing when carrying.According to these prescriptions, the generation ratio that can carry out the height circulationization of moulding and reduce the bad phenomenon of silver-colored spot (シ Le バ one) etc.In addition, coating of particles can be the general shape of cylindrical, corner post shape, sphere etc., and is more preferably cylindrical.The diameter of preferred this cylinder is 1～5mm, and more preferably 1.5～4mm further is preferably 2～3.3mm.On the other hand, the length of cylinder is preferably 1～30mm, and more preferably 2～5mm further is preferably 2.5～3.5mm.
< about the moulding article that form by resin combination of the present invention >
The flame retardant resin composition of the present invention that obtains as stated can produce various products through the particle of making is as stated carried out injection molding usually.And, also can be without granulation, with forcing machine directly with the resin manufacture slabbing behind the melting mixing, film like, special-shaped extrusion molding article, blowing (direct blow) moulding article and injection-molded article.
In above-mentioned injection molding; Not only can adopt common forming method; Can also be according to purpose; Suitably adopt injection compression molding, injection pressure moulding, air-auxiliary injection forming, foaming (comprising the moulding of injecting), insert moulding through supercutical fluid, in-mold coating (In-Mold Coating) moulding, heat insulation mould molding, the injection moulding of heating cooling mould molding, dual-color forming, interlayer moulding, ultra-high speed injection molding etc. rapidly, thereby obtain the moulding article.The advantage of these various manufacturing process is all known.In addition, moulding can be selected any in cold runner mode and the hot runner mode.
In addition, resin combination of the present invention also can become forms such as various special-shaped extrusion molding articles, sheet, film like and be used through extrusion moulding.In addition, in sheet, film like moulding, can also use blow moulding, rolling process, casting method etc.And, through implementing specific extension operation, also can be shaped to heat-shrinkable tube.In addition, also can resin combination of the present invention be manufactured the moulding article through rotoforming or blow molding etc.
The moulding article of the resin combination with excellent outward appearance and hydrolytic resistance so, can be provided.That is, according to the present invention, provide flame retardant resin composition melt molding and the moulding article that form in addition, said resin combination is made up of the A composition of 100 weight parts, the B composition of 0.1～0.2 weight part and the C composition of 0.001～20 weight part.
And, to the moulding article that form by flame retardant resin composition of the present invention, can carry out various surface treatments.In this said surface treatment; Be meant that the surface at synthetic resin of vapor deposition (physical vapor deposition, cvd etc.), plating (electric plating, plated by electroless plating, fusion plating etc.), application, coating, printing etc. forms the processing of new coating, can use the method that is generally used for polycarbonate resin.As surface treatment, can enumerate the various surface treatments of hard coat, hydrophobic oleophobic coating, UVA coating, infra-red absorption coating, metallic coating (vapor deposition) etc. particularly.
Embodiment
The present inventor thinks best embodiment of the present invention at present, and the embodiment for the preferable range that satisfies above-mentioned each important document for example, is recorded in its typical example among the following embodiment.Certainly, the present invention is not limited to these embodiments.
Below, specify the present invention through embodiment.In addition, evaluation is to carry out according to following method.
(1) flame retardant resistance: use hot air dryer, under 120 ℃ to carry out 6 hours drying through following method resulting granules.Then; Through injection moulding machine (IS150EN-5Y, toshiba machine (strain) make), be that 280 ℃, die temperature are under 60 ℃ the condition at barrel temperature; Molding thickness is the test film that the UL94 combustion test of 2mm is used, and implements the testing vertical flammability of UL specification 94 and estimates.To not meeting the test film of any one grade among V-0, V-1, the V-2, be designated as not V.
(2) total light transmittance: use hot air dryer, under 120 ℃ to carry out 6 hours drying through following method resulting granules.Then; With injection moulding machine (SG-150U; Sumitomo Heavy Industries, Ltd makes); At barrel temperature is that 290 ℃, die temperature are under 80 ℃ the condition, with 50 seconds moulding circulation make wide 50mm, long 90mm, thick be that to begin from spout (ゲ one ト) side be the syllogic plate of 3mm (long 20mm), 2mm (long 45mm), 1mm (long 25mm).Use the reflecting & transmitting rate appearance HR-100 of Murakami K. K.'s dye technology institute system, measure the total light transmittance of the thickness 2.0mm profiled sheeting partly of this syllogic plate according to JIS K 7105-1.
(3) summer is than shock strength: use hot air dryer, under 120 ℃ to carry out 6 hours drying through following method resulting granules.Then; Through injection moulding machine (SG-150U, Sumitomo Heavy Industries, Ltd make), be that 330 ℃, die temperature are under 80 ℃ of conditions at barrel temperature; Make mensuration with 50 seconds moulding circulation and use test film, carry out the mensuration of breach summer than shock strength according to ISO 179.
Embodiment 1～22 and comparative example 1～5
In the polycarbonate resin powder of making by the dihydroxyphenyl propane photoreactive gas through interface polycondensation; Each use level by record in the table cooperates various additives, and after mixing with mixing machine, (TEX30 α is (meshing fully with the exhaust biaxial extruder; Equidirectional rotation; The double thread screw rod), Japan Steel Co., Ltd makes) carry out melting mixing, thus obtain particle.Additive with 10 times concentration of use level, behind the premixture with Henschel mixer making and polycarbonate resin powder, all mixes with mixing machine respectively in advance.Extrusion condition is extrusion capacity: 20kg/h; Screw rod rotation number: 150rpm; Exhaust portion vacuum tightness: 3KPa; Extrusion temperature: from first supplying opening to overflow mould is 260 ℃.
Shown in the theing contents are as follows of each composition of the symbolic representation in the table.
(A composition)
PC-1: through interface polycondensation; Stop p-tert-butylphenol, phosgene synthetic straight chain aromatic polycarbonate resin powder (the パ Application ラ イ ト L-1225WP (trade(brand)name) of agent by dihydroxyphenyl propane, as end; Viscosity-average molecular weight is 22400, and Teijin Chemicals, Ltd. makes)
PC-2:, stop p-tert-butylphenol, the phosgene synthetic straight chain aromatic polycarbonate resin powder (L-1225WX (trade(brand)name), viscosity-average molecular weight is 19700, Teijin Chemicals, Ltd.'s manufacturing) of agent by dihydroxyphenyl propane, as end through interface polycondensation
PC-3: through melting state transesterification reaction, (viscosity-average molecular weight is 22500, and this chain link components in proportions is passed through to prop up the chain link composition is about 0.1 mole of % in repeating unit weight polycarbonate resin particle by dihydroxyphenyl propane and diphenyl carbonate synthetic 1H-NMR measures and calculates, and is 0 mole of % (not having corresponding peak) in the PC-1 polycarbonate resin that use the same manner is measured)
PC-4:, stop p-tert-butylphenol, the phosgene synthetic straight chain aromatic polycarbonate resin powder (CM-1000 (trade(brand)name), viscosity-average molecular weight is 16000, Teijin Chemicals, Ltd.'s manufacturing) of agent by dihydroxyphenyl propane, as end through interface polycondensation
(B composition)
B-1: Port リ Off ロ Application MPA FA500 (trade(brand)name) (ltd. makes for tetrafluoroethylene, DAIKININDUSTRIES)
B-2:POLY TS AD001 (trade(brand)name) (PIC society makes, the mixture (polytetrafluoroethylene content be 50 weight %s) of this tetrafluoroethylene class mixture for being made up of polytetrafluoroethylparticle particle and styrene-acrylonitrile copolymer particle)
B-3:Blendex449 (trade(brand)name) (Cronpton makes, the mixture (polytetrafluoroethylene content be 50 weight %s) of this tetrafluoroethylene class mixture for being made up of polytetrafluoroethylparticle particle and styrene-acrylonitrile copolymer particle)
B-4: メ タ Block レ Application A3700 (trade(brand)name) (Mitsubishi Rayon Co.Ltd. makes, the mixture (content of tetrafluoroethylene be 50 weight %s) of this tetrafluoroethylene class mixture for being made up of the tetrafluoroethylene acrylic copolymer)
(C composition)
C-1: メ ガ Off ア Star Network F-114P (trade(brand)name) (potassium perfluorobutane sulfonate salt, Dainippon Ink and Chemicals, Inc makes)
C-2:KSS (trade(brand)name) (sulfobenzide-3, the single disulfonic acid potassium salt of 3 '-disulfonic acid di-potassium and sulfobenzide-3-is with 2:8 blended mixture, コ one シ one PVC one ジ ヤ パ Application is made)
C-3: the straight chain shape silicon compound that contains Si-H and phenyl
(method of manufacture of C-3)
In the 1L flask that has whisking appliance, refrigerating unit, TM, add entry 301.9g and toluene 150g, and interior temperature is cooled to 5 ℃.In tap funnel, drop into the mixture of trimethylchlorosilane 21.7g, dimethyl dichlorosilane (DMCS) 23.0g, dimethyldichlorosilane(DMCS) 12.9g and diphenyl dichlorosilane 76.0g, and when stirring, in flask, dripped with 2 hours.In the meantime, continue to cool off, so that interior temperature maintains below 20 ℃.Drip after the end, continuation is stirred down for 20 ℃ in interior temperature and was carried out slaking in 4 hours.Then, leave standstill and remove isolating hydrochloric acid water layer, add 10% aqueous sodium carbonate and stir after 5 minutes, leave standstill and remove isolating water layer.Then, further clean 3 times, confirm that toluene layer becomes neutrality with ion exchanged water.This toluene solution under reduced pressure is heated to 120 ℃ of interior temperature, thereby after removing toluene and low boilers,, obtains silicon compound C-3 through removing by filter insolubles.
Among this silicon compound C-3, the Si-H amount is that 49 weight %, mean polymerisation degree are 8.0 for 0.21mol/100g, aromatic series base unit weight.
C-4: the silicon compound that contains Si-H, phenyl, branched structure
(method of manufacture of C-4)
In the 1L flask that has whisking appliance, refrigerating unit, TM, add 1; 1,3,3-tetramethyl disiloxane 100.7g, 1; 3; 5,7-tetramethyl-ring tetrasiloxane 60.1g and octamethylcyclotetrasiloxane 129.8g, octaphenyl cyclotetrasiloxane 143.8g and phenyltrimethoxysila,e 99.1g, and add vitriol oil 25.0g while stirring.After interior temperature is cooled to 10 ℃, while stirring with 30 fens water 13.8g that drip in the clockwise flask.In the meantime, continue to cool off, so that interior temperature maintains below 20 ℃.Drip after the end, continuation is stirred down for 10～20 ℃ in interior temperature and was carried out slaking in 5 hours.Then, add water 8.5g and toluene 300g and stir after 30 minutes, leave standstill and remove isolating water layer.Then, further clean 4 times, confirm that toluene layer becomes neutrality with 5% aqueous sodium persulfate solution.This toluene solution under reduced pressure is heated to 120 ℃ of interior temperature, thereby after removing toluene and low boilers,, obtains silicon compound C-4 through removing by filter insolubles.
Among this silicon compound C-4, the Si-H amount is that 30 weight %, mean polymerisation degree are 10.95 for 0.50mol/100g, aromatic series base unit weight.
< the signal formula of each silicon compound >
C-3：M 2D H 2D 1D φ2 3
C-4：M H 3D H 2D 3.5D φ2 1.45T φ 1
In addition, the following siloxane unit of each symbolic representation in the above-mentioned signal formula, the coefficient of each symbol (index number) are the quantity (polymerization degree) of each siloxane unit in expression 1 molecule.
M：(CH 3) 3SiO 1/2
M H：H(CH 3) 2SiO 1/2
D：(CH 3) 2SiO
D H：H(CH 3)SiO
D φ2：(C 6H 5) 2SiO
T φ：(C 6H 5)SiO 3/2
C-5:PX-200 (trade(brand)name) (Resorcinol two (two xylyl SULPHOSUCCINIC ACID ESTERs), big eight chemical industry (strain) are made)
(other)
SL: リ ケ マ one Le SL900 (trade(brand)name) (LTD makes for polyunsaturated fatty acid ester class releasing agent, RIKENVITAMIN CO.)
CS:ECS-03T-511 (trade(brand)name) (NEG (strain) is made for spun glass, diameter 13 μ m, cutting length 3mm)
MF:PEF-301S (trade(brand)name) (day east is spun (strain) and made for glass chopped strand, diameter 9 μ m, number average fiber length 30 μ m)
TMP:TMP (trade(brand)name) (Phosphorus stablizer, big eight chemical industry (strain) are made)
Figure BSA00000614743900321
Figure BSA00000614743900331
Figure BSA00000614743900341
Figure BSA00000614743900351
Can know clearly that from above-mentioned table 1 and table 2 flame retardant resin composition of the present invention has the transparency (total light transmittance of certain limit) of specified range, compare that the shock strength during high-temperature molding is excellent with comparative example.
Industrial applicibility
Flame retardant resin composition of the present invention; The transparency with certain limit; And flame retardant resistance, outward appearance are excellent, can create the high aesthetic appearance of delicate mist degree that the transparency of certain limit is brought, therefore; Be applicable to that it reaches very special effect in various electronic apparatuss, OA machine, vehicle part, mechanical part, other the various uses of Agricultural Materials, transport container, game machine and groceries etc. in industry.

Claims (8)

  1. One kind when the moulding resin compsn, the transparency that makes resulting moulding article reaches 74～87% method in the total light transmittance of being measured by the thick profiled sheeting of 2mm, wherein,
    As resin combination; Use comprise as the aromatic polycarbonate resin of A composition, as the B composition have that fibril forms the tetrafluoroethylene of ability and as the fire retardant of C composition; And; With respect to the aromatic polycarbonate resin as the A composition of 100 weight parts, as the B composition to have the tetrafluoroethylene that fibril forms ability be 0.1～0.2 weight part, be 0.001～20 weight part as the fire retardant of C composition.
  2. 2. the method for claim 1, wherein the B composition is the tetrafluoroethylene that fibril forms ability that has of mixed style.
  3. 3. the method for claim 1, wherein the content of C composition is 0.001～5 weight part.
  4. 4. the method for claim 1, wherein the content of C composition is 0.01～0.3 weight part.
  5. 5. the method for claim 1, wherein the C composition is the organic metal salt based flame retardant.
  6. 6. method as claimed in claim 5, wherein, the organic metal salt based flame retardant is organic acid an alkali metal salt or alkali earth metal salt.
  7. 7. flame retardant resin composition as claimed in claim 6, wherein, organic acid an alkali metal salt or alkali earth metal salt are organic sulfonic acid an alkali metal salt or organic sulfonic acid alkali earth metal salt.
  8. 8. method as claimed in claim 5, wherein, the C composition is fluorine-containing organic metal salt based flame retardant.
CN201110364807XA 2007-05-31 2008-05-26 Flame-resistant polycarbonate resin composition Pending CN102432989A (en)

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JP5371641B2 (en) * 2009-09-04 2013-12-18 株式会社Ａｄｅｋａ Flame retardant polycarbonate resin composition
EP2562217B1 (en) * 2010-04-20 2017-05-10 Mitsubishi Gas Chemical Company, Inc. Transparent, fire-retardant aromatic polycarbonate resin composition and molded product
JP5679693B2 (en) * 2010-05-07 2015-03-04 帝人株式会社 Flame retardant polycarbonate resin composition
JP5558926B2 (en) * 2010-06-01 2014-07-23 帝人株式会社 Flame retardant polycarbonate resin composition
US8927633B2 (en) 2011-09-02 2015-01-06 Mitsubishi Gas Chemical Company, Inc. Aromatic polycarbonate resin composition, and molded article comprising same
JP2015199853A (en) * 2014-04-09 2015-11-12 三菱エンジニアリングプラスチックス株式会社 polycarbonate resin composition and molded article
CN109777073B (en) * 2019-01-24 2021-07-16 金发科技股份有限公司 Polycarbonate compositions and use of sulfonate and phosphorus-containing compounds to reduce fuming and heat release in polycarbonates

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